Dianthraquinonylamine sulphonic acid dyestuff



Patented Nov. 12,1929

UNITED srA'rEs PATENT OFFICE wanna me, or vonwrnxnn, AND nnmmcn manna, or 'nnvnaxusmr, rm

COLOGNE, GERMANY, ASSIGNORS TO GENERAL ANILIN'E WORKS,'ING., OF m YOB Iy N. Y., CORPORATION OF DELAWARE DIANTHRAQUINONYLAMINE SULPH ONIC ACID DYES'IUFI A 80 Drawing. Application filed August 17, 1825, flerial Io. 50,888, and Germany September 27,

We have invented new and useful improvements in dianthraquinonylamine sulphonic acid dyestufi's.

Our inventionconsists in the sulphonation of dianthraquinonylamines and in the substantially pure dianthraquinonylamine sul honic acids obtained by our novel rocess. ianthraquinonylamines ha gIt e general formula C ,H,O,NH8: ,0, have first been produced by condensing aminoanthraquinones with halo en anthraquinones. This reaction, as well as t e products obtained byit,aredescribed for instance in U. S. Patent #814,137.. It is stated in this patent that by treating dianthraquinonylamines with sulphqnating agents at temperatures from 100130 0., dyestuffs are produced which d e wool from an acid bath, fast shades. his reaction has, however, never found any practical application.

We have now found that the treatment of unsubstituted dianthraquinonylamines as stated in the above mentioned patent with sulphonating agents, is a very complex reaction and that a mixture of different comunds is formed, which produces on animal A bres unsightly andvalueless shades. The

two main reactions involved inthe treatment of dianthraquinonylamines with sulphonat- 3o ing agents consists in a straight sul honation and in a joint sulphonation and oxi ation.

-' We have now found that sul honation proceeds at lower temperatures, an we have further found the correct conditions whereby straight dianthra uinonylamine sul honic acids are produce without the pro uction of any substantial amounts of oxidation products; substantially urefdianthrziquinonylamine sulphonic aci s.can'be recovered 40 directly from the reaction.

The dyeing properties, particularly shades, of the new products are quite different from those of the old mixed sulphonation products or from the oxy-dianthraquinon lamine sulphonic acids described in our nitedStates Patent N 0. 1,564,091 filed'at even date. The novel,\straight dianthraquinon lamine sulphonic acids are furthermore 'stinguished by a very characteristic reaction. Addition of formaldehyde to their solutions in con-v centrated sulfuric acid produces ainarked change in the color of these solutions. -In

the case of the oxy-dianthraquinonylamine sulphonic acids nosuch change of color occurs.

The process of producing our novel dianthraquinonylamine sulphonic acids consists in treating dianthraquinonylamines' with moderatel concentrated fuming sulfuric acid,.i. e., uming sulfuric acid containing not more than 30% free S0,, attemperatures below 100 C. 'It is possible by varying the concentrations, temperatures, etc. within the above conditions, to obtain mono, di, and

eventually higher sulphonated dianthraquinonylamine su phonic acids. Preferably, temeratures between to C. are used.

or the production of the acids. .Practicall' I the conditions escribed herein, and the poly-sulphonic no oxidation occurs under straight sul hom'c acids obtained are practically free rein hydroxy-dianthraquinonylamine sulphonic acidsand other oxidation products. I p I The novel straight dianthraquinon lamine sulphonic acids arein the form of th orange to yellowish brown colors, nearly in- 16 eir sodium salts brownish-red, crystalline substances, diflicultly soluble in water with from in concentrated sulfuric acid withv from reddish-brown to violet-blue colors. Addition of formaldehyde, as well as addition of boric acid to-these solutions completely changes their colors. Our new products dye animal fibres from an acid bath from orange to yellowish-brown colors.

The dianthraquinonylamines particularly suited for our novel process are, the 1-1 'dianthraquinonylamine, having most probably the following formula and the l -2-dianthraquinonylamine of the probable formula,

coo

1 co NH 15% oleumand heated for a short time to 95100 C. until a test sample is completely soluble in hot water with a yellowish-brown color. Thecooled metal is then stirred, without any further cooling, into 1000 parts water. Saturated'sodium chloride solution is then added atboiling temperature until a test simple, after cooling, shows that the dyestufi is completely salted out. The product is after cooling filtered off, washed to neutrality with Q dilute sodium chloride solution and dried.

The product so obtained is substantially free from oxidation products and is the sodium "salt of a disulphonic acid, having. most probably the formula It can be called the 1-1-dianthraquinonylamine-44 disul honate of sodium.

The product 18 somewhat soluble in cold water, more easily soluble in hot water with tion of boric acid to reddish-violet. It dyes wool in an acid bath exceedingly fast yellowish-brown shades, which are not changed by afterchroming. The same shade is obtained on chrome mordanted wool.

Ewample 2.-,-10 parts 1-1-dianthraquinonylamine are treated for a short time at 30 C. with 100 parts 25% oleum. The melt is drowned in water, salted out, filtered off and dried. It is probably 1-1-dianthraquinonylamine -sulphonic acid, being very diflicultly soluble in water, soluble in strong sulfuric acid with a reen coloration, turning to blueafter the ad ition of formaldehyde, dyeing wool from an acid bath reddish-brown fast shades.

Example 3.10 parts 1-2-dianthraquinonylamine are treated for a short time at 95- 100 C. with 100 arts 15% oleum, until the product is entire y soluble in water. The

. melt is poured into water, salted out, filtered and dried.

The dyestuil obtained is the sodium salt of a 1-2-dianthra uinonylamine disulphonic acid. It is a red ish-brown, crystalline powder, diflicultly soluble in cold water, somewhat better soluble in hot water with an oran ge color. It is soluble in concentrated sulfuric acid with a deep violet-blue color, which turns to a ure violet by the addition of formaldehy e. It dissolves in concentrated sulfuric acid containing boric acid with a reddish-violet color. It dyes wool in an acid bath, clear yellowish-orange shades of excellent fastness properties.

We claim:

1. The process of sulphonating 1-1-dianthraquinonylamine with fuming sulfuric acid containing not more than 30% free SO at temperatures below 100 C.

2. In processes of producing 1-1'-dianthraquinonylamine-e-'-disulphonic acid the step comprising sulphonating 1-1 '-dianthraquinonylamine with oleum containing not more than 30% free S0 and at temperatures between 80 and 100 C.

3. As new products the compounds of the probable formula:

wherein as stands for hydrogen or a sulphonic acid group, said compounds being soluble in strong sulfuric acid with green to reddishbrown colorations, turning to blue after the addition of formaldehyde, dyeing wool from an acid bath reddish-brown to yellowishbrown shades.

5 In testimony whereof we have hereunto set our hands. I

WALTER MIEG. HEINRICH RAEDER. 

